Polypeptoid Monomer Sequence and Chemical Composition as Independent Controls of Interfacial Tension and Elasticity at Air/Fluid Interfaces.

We use sequence-specific polypeptoids to characterize the impact of the monomer sequence on the adsorption of surface-active polymers at fluid/fluid interfaces. Sets of 36 repeat unit polypeptoids with identical chemical composition, but different sequences of hydrophobic moieties along the oligomer chain (taper, inverse taper, blocky, and evenly distributed), are designed and characterized at air/water interfaces. Polypeptoids are driven to the interfaces by decreasing the solvent quality of the aqueous solution.

Nonequilibrium structure formation in electrohydrodynamic emulsions.

Application of an electric field across the interface of two fluids with low, but non-zero, conductivities gives rise to a sustained electrohydrodynamic (EHD) fluid flow. In the presence of neighboring drops, drops interact the EHD flows of their neighbors, as well as through a dielectrophoretic (DEP) force, a consequence of drops encountering disturbance electric fields around their neighbors. We explore the collective dynamics of emulsions with drops undergoing EHD and DEP interactions.

Solvent Quality and Aggregation State of Asphaltenes on Interfacial Mechanics and Jamming Behavior at the Oil/Water Interface.

The formation of highly stable water-in-oil emulsions results in complications in both upstream and downstream processing. Emulsion stability in these systems has been connected to the adsorption of surface-active asphaltenes that are assumed to form a rigidified film at the oil/water (o/w) interface. Full characterization of this behavior is needed to allow for engineered solutions for enhanced oil recovery.

Highly Conductive Polyoxanorbornene-Based Polymer Electrolyte for Lithium-Metal Batteries.

This present study illustrates the synthesis and preparation of polyoxanorbornene-based bottlebrush polymers with poly(ethylene oxide) (PEO) side chains by ring-opening metathesis polymerization for solid polymer electrolytes (SPE). In addition to the conductive PEO side chains, the polyoxanorbornene backbones may act as another ion conductor to further promote Li-ion movement within the SPE matrix. These results suggest that these bottlebrush polymer electrolytes provide impressively high ionic conductivity of 7.

Synergistic Effects of Multiple Excipients on Controlling Viscosity of Concentrated Protein Dispersions.

Viscosity control is essential for the manufacturing and delivery of concentrated therapeutic proteins. Limited availability of the precious protein-based drugs hinders the characterization and screening of the formulation conditions with new types or different combinations of excipients. In this work, a droplet-based microfluidic device with incorporated multiple particle tracking microrheology (MPT) is developed to quantify the effects of two excipients, arginine hydrochloride (ArgHCl) and caffeine, on the viscosity of concentrated bovine gamma globulin (BGG) dispersions at two different values of pH.

3D Printing of Liquid Metal Embedded Elastomers for Soft Thermal and Electrical Materials.

Liquid metal embedded elastomers (LMEEs) are composed of a soft polymer matrix embedded with droplets of metal alloys that are liquid at room temperature. These soft matter composites exhibit exceptional combinations of elastic, electrical, and thermal properties that make them uniquely suited for applications in flexible electronics, soft robotics, and thermal management. However, the fabrication of LMEE structures has primarily relied on rudimentary techniques that limit patterning to simple planar geometries.

Shear-Modulated Rates of Phase Transitions in Sphere-Forming Diblock Oligomer Lyotropic Liquid Crystals.

Hydration of the amphiphilic diblock oligomer CH(CHCHO)OH (CE) leads to concentration-dependent formation of micellar body-centered cubic (BCC) and Frank-Kasper A15 lyotropic liquid crystals (LLCs). Quiescent thermal annealing of aqueous LLCs comprising 56-59 wt % CE at 25 °C after quenching from high temperatures established their ability to form short-lived BCC phases, which transform into long-lived, transient Frank-Kasper σ phases en route to equilibrium A15 morphologies on a time scale of months. Here, the frequency and magnitude of applied oscillatory shear show the potential to either dynamically stabilize the metastable BCC phase at low frequencies or increase the rate of formation of the A15 to minutes at high frequencies.

Droplet-Based Microfluidic Tool to Quantify Viscosity of Concentrating Protein Solutions.

Purpose: Measurement of the viscosity of concentrated protein solutions is vital for the manufacture and delivery of protein therapeutics. Conventional methods for viscosity measurements require large solution volumes, creating a severe limitation during the early stage of protein development. The goal of this work is to develop a robust technique that requires minimal sample.

Inflammation product effects on dilatational mechanics can trigger the Laplace instability and acute respiratory distress syndrome.

In the lungs, the Laplace pressure, ΔP = 2γ/R, would be higher in smaller alveoli than larger alveoli unless the surface tension, γ decreases with alveolar interfacial area, A, such that 2ε > γ in which ε = A(dγ/dA) is the dilatational modulus. In Acute Respiratory Distress Syndrome (ARDS), lipase activity due to the immune response to an underlying trauma or disease causes single chain lysolipid concentrations to increase in the alveolar fluids via hydrolysis of double-chain phospholpids in bacterial, viral, and normal cell membranes. Increasing lysolipid concentrations decrease the dilatational modulus dramatically at breathing frequencies if the soluble lysolipid has sufficient time to diffuse off the interface, causing 2ε < γ, thereby potentially inducing the "Laplace Instability", in which larger alveoli have a lower internal pressure than smaller alveoli.

Insensitivity of Sterically Defined Helical Chain Conformations to Solvent Quality in Dilute Solution.

The interplay between polymer-polymer and polymer-solvent interactions as well as interactions that impose secondary structures determines the conformation of polymer chains in dilute solution. Polypeptoids-poly(-substituted glycines) have been shown to form helical secondary structures primarily driven by steric interactions from chiral, bulky side chains, while polypeptoids with a racemic mixture of the same side chains lead to unstructured coil chains with a shorter Kuhn length. Small-angle neutron scattering (SANS) of the polypeptoids in dilute solution reveals that the helical polypeptoids are only locally stiffer than the coil chains formed from the racemic analogue, but exhibit overall flexibility.

Transport of Flexible, Oil-Soluble Diblock and BAB Triblock Copolymers to Oil/Water Interfaces.

The connection between block copolymer architecture and adsorption at fluid/fluid interfaces is poorly understood. We characterize the interfacial properties of a well-defined series of polyethylene oxide/polydimethyl siloxane (PDMS) diblock and BAB triblock copolymers at the dodecane/water interface. They are oil-soluble and quite flexible because of their hydrophobic PDMS block.

Dynamic interfacial tension measurement under electric fields allows detection of charge carriers in nonpolar liquids.

Hypothesis: Electric fields enhance surfactant transport to oil-water interfaces when the surfactant forms charged aggregates in the oil phase. Hence, transport under electric fields could be used to detect charged surfactant aggregates in nonpolar media.

Experiments: Two surfactants with different architecture were dispersed in Isopar-M.

Electric fields enable tunable surfactant transport to microscale fluid interfaces.

The transport dynamics of oil-soluble surfactants to oil-water interfaces are quantified using a custom-built electrified capillary microtensiometer platform. Dynamic interfacial tension measurements reveal that surfactant transport is enhanced under a dc electric field, due to electro-migration of charge carriers in the oil toward the interface. Notably, this enhancement can be precisely tuned by altering the field strength and temporal scheduling.

Colloidal stability dictates drop breakup under electric fields.

Electric fields can deform drops of fluid from their equilibrium shape, and induce breakup at sufficiently large field strengths. In this work, the electric field induced breakup of a squalane drop containing a colloidal suspension of carbon black particles with polyisobutylene succinimide (OLOA 11000) surfactant is studied. The drop is suspended in silicone oil.

Interfacial Properties of Polyelectrolyte-Surfactant Aggregates at Air/Water Interfaces.

The transport, equilibrium properties, and mechanics of stable, rodlike surfactant-polyelectrolyte aggregates, poly(cetyltrimethylammonium vinyl benzoate) or pCTVB, are characterized at air/water interfaces for bulk concentrations near and below the critical aggregation concentration. The surfactant drives the transport to air/water interfaces, while the polyelectrolyte provides elasticity to the coated interfaces and appears to remain adsorbed after the bulk solution is exchanged with water. The processing of interfaces is shown to allow the interfacial tension of the interface to be changed significantly while maintaining a high dilatational elasticity.

Microfluidic Droplet-Based Tool To Determine Phase Behavior of a Fluid System with High Composition Resolution.

The goal of this work is to develop a simple microfluidic approach to characterizing liquid-liquid phase behavior in complex aqueous mixtures of organics and salts. We take advantage of the permeability of inexpensive microfluidic devices to concentrate aqueous solutions on chip. We demonstrate a technique that allows phase boundaries to be identified with high compositional resolution and small sample volumes.

Formation and elasticity of membranes of the class II hydrophobin Cerato-ulmin at oil-water interfaces.

Protein surfactants show great potential to stabilize foams, bubbles, and emulsions. An important family of surface active proteins, the hydrophobins, is secreted by filamentous fungi. Two hydrophobin classes have been recognized, with Class II exhibiting slightly better solubility than Class I, although neither is very soluble in water.

Effect of surfactant tail length and ionic strength on the interfacial properties of nanoparticle-surfactant complexes.

Mixed nanoparticle-surfactant systems are effective foam stabilizing agents, but the lack of colloidal stability of the bulk dispersions makes interfacial characterization challenging. This study investigates the adsorption of CTAB/SiO complexes at air/water interfaces through surface tension and interfacial rheology measurements. The effects of surfactant tail length, ionic strength, and interfacial processing on the surface properties are measured utilizing a bulk reservoir exchange methodology to avoid bulk destabilization.

Droplet-based characterization of surfactant efficacy in colloidal stabilization of carbon black in nonpolar solvents.

Development of an electrostatic stabilization mechanism for colloidal suspensions in nonpolar fluids requires an improved understanding of the interactions between the inverse micelles and particles as well as the roles that steric and electrostatic effects play. A droplet-based millifluidic device is designed and used to investigate the stabilization effects of surfactants on colloidal suspensions. A system containing carbon black and the surfactant OLOA 11000 suspended in dodecane is chosen as a well-characterized system to study sedimentation quantitatively.

Formation of a Rigid Hydrophobin Film and Disruption by an Anionic Surfactant at an Air/Water Interface.

Hydrophobins are amphiphilic proteins produced by fungi. Cerato-ulmin (CU) is a hydrophobin that has been associated with Dutch elm disease. Like other hydrophobins, CU stabilizes air bubbles and oil droplets through the formation of a persistent protein film at the interface.

Measurements of Submicron Particle Adsorption and Particle Film Elasticity at Oil-Water Interfaces.

The influence of particle adsorption on liquid/liquid interfacial tension is not well understood, and much previous research has suggested conflicting behaviors. In this paper we investigate the surface activity and adsorption kinetics of charge stabilized and pH-responsive polymer stabilized colloids at oil/water interfaces using two tensiometry techniques: (i) pendant drop and (ii) microtensiometer. We found, using both techniques, that charge stabilized particles had little or no influence on the (dynamic) interfacial tension, although dense silica particles affected the "apparent" measured tension in the pendent drop, due to gravity driven elongation of the droplet profile.

Transport of nanoparticulate material in self-assembled block copolymer micelle solutions and crystals.

Water soluble poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) [PEO-PPO-PEO] triblock copolymers self-assemble into thermoreversible micellar crystals comprised of periodically spaced micelles. The micelles have PPO cores surrounded by hydrated PEO coronas and the dimensions of the unit cell of the organized micelles is on the order of several to tens of nanometers. Fluorescence recovery after photobleaching (FRAP) is used to quantify nanoparticle transport in these nanostructured polymer micelle systems.

Sequential adsorption of an irreversibly adsorbed nonionic surfactant and an anionic surfactant at an oil/aqueous interface.

Aerosol-OT (AOT) and Tween 80 are two of the main surfactants in commercial dispersants used in response to oil spills. Understanding how multicomponent surfactant systems interact at oil/aqueous interfaces is crucial for improving both dispersant design and application efficacy. This is true of many multicomponent formulations; a lack of understanding of competition for the oil/water interface hinders formulation optimization.

Coalescence behavior of oil droplets coated in irreversibly-adsorbed surfactant layers.

Coalescence between oil caps with irreversibly adsorbed layers of nonionic surfactant is characterized in deionized water and electrolyte solution. The coalescence is characterized using a modified capillary tensiometer allowing for accurate measurement of the coalescence time. Results suggest two types of coalescence behavior, fast coalescence at low surface coverages that are independent of ionic strength and slow coalescence at high coverage.

Controlling thread formation during tipstreaming through an active feedback control loop.

Microscale tipstreaming is a hydrodynamic phenomenon capable of producing submicron sized droplets within a microfluidic device. The tipstreaming process results in the drawing of a thin thread from a highly curved interface and occurs as a result of interfacial surfactant concentration gradients that develop due to elongational flows generated within flow focusing geometries. However, in conventional microfluidic devices, the thread formation is periodically interrupted by the formation of larger primary droplets.